Hydrogen manufacture using centrifugal compressors

ABSTRACT

A PROCESS FOR MANUFACTURING HIGH PRESSURE, HIGH PURITY HYDROGEN WHICH COMPRISES: (A) GENERATING BY STEAM REFORMING OR PARTIAL OXIDATION OF HYDROCARBONS AT A PRESSURE BELOW ABOUT 450 P.S.I.G. A HYDROGEN-RICH GAS CONTAINING SUFFICIENT CO2 SO THAT THE MOLECULAR WEIGHT OF THE HYDROGEN-RICH GAS IS AT LEAST FOUR; (B) CENTRIFUGALLY COMPRESSING THE HYDROGEN-RICH GAS FROM THE PRESSURE BELOW ABOUT 450 P.S.I.G. TO A SUBSTANTIALLY HIGHER PRESSURE ABOVE 450 P.S.I.G. TO OBTAIN HIGH PRESSURE HYDROGEN-RICH GAS; (C) REMOVING CO2 FROM THE HIGH PRESSURE HYDROGEN-RICH GAS TO OBTAIN HIGH PURITY HYDROGEN, AT LEAST PART OF THE CO2 BEING REMOVED BY ABSORBING CO2 IN A PHYSICAL ABSORBENT.

Apri-l 2, 1974 c. s. SMITH ETAL HYDROGEN MANUFACTURE USING CENTRIFUGAL COMPRESSORS Original Filed May 17, 1968 S--S O l. 20D

f 'HYDROGEN USING. f .-.cENTRIr-UGAL CQMPREssoRs.

to,.Calif., -assignors to Chevron Research Company, San Fran- .cisocl Original application May 17, 1968, Ser. No. 736,520, now i 'Patent No. 6,518,331. Divided and this application June 26, 1970, Ser. No. 59,864A i f' The portion'fofvthe term of the patent subsequent to 1 1.6, 1987, has been disclaimed f Cl..01b 1/16, 1/32, 31/20 ILS..Cll2.3f650` v ABSTRACT oF ,THE DrsCLosURE f 'Apro'cess vformanufacturing high pressure, highpurity hydrogen'which comprises: (a) gener'ating'bysteam reforming'orpartial oxidation of fhydrocarbons at a pressure-below about 450 p.s.i.g. a hydrogen-rich gas containinglsuiicient CO2 so that the molecular weight of the hydrogen-rich gas is at least (b): centrifugally compressing the hydrogen-rich gas from the pressure below about.450'p.s:i.g. to a substantially higherpressure above 450 p.s.i;g. to obtain high pressure hydrogen-rich gas;

(c) removing CO2 from the high pressure hydrogen-rich vgas to obtain high purity hydrogen, atleast part of the CO2 being removedV by 'absorbing COzin a physical absorbent.:l 't l CRoss REFERENCES .v `application is a division vo f Ser. No. 736,520, tiled May-@17, v1968, now U.S. Pat. No. 3,618,331, which in 'United States Patent .4 claims in a hydroconversion process. By hydroconversion process is meanta process wherein hydrogen-is reacted with hydrocarbons'so as to convert the hydrocarbons to more desirable hydrocarbons or hydrocarbon products.

2. Description of the prior art A; Means for obtain-ing raw, hydrogenrich gas-There 'are a number of current processes available for the production of raw hydrogen. Many of these processes use .hydrocarbons as a source of hydrogen. Twoof the most widely practiced methods of obtaining raw, hydrogen-rich .gas are steam Vreforming and partial oxidation.

In typical steam reforming processes, hydrocarbon feed is pretreatedv to remove sulfur compounds which are poisons to the vreforming catalyst. The d esulfurized feed is mixed with steam and then is passed through tubes con- -nacei heats the reactants Vin the'tubes to temperatures of L200-.1,7009 FrrPressures-maintained in the reforming .furnace tubes range 4from atmospheric -to 450 p.s.i.g. If

ay secondary furnaceor. reactorris employed, pressures .used ,for ref (n'rriing may be, as highas450 p.s.i.g. to 700 ,pai-s In ssdsryreformer. readers .Part sith@ hydfs- ICC carbons in the effluent from the primary reformer is burned with oxygen. Because of the added expense, secondary. reformers are generally not used in hydrogen manufacture but are used where it is desirable to obtain a mixture of H2 and N2, as in ammonia manufacture. Thebasic reactions in the steam reforming process are:

Because the hydrogen product is used in high-pressure processes, it is advantageous to operate at high pressure to avoid high compression requirements. However, high pressures are adverse to the equilibrium; and higher temperatures must be employed. Consistent with hydrogen purity requirement of about to 97 volume percent H2 in the final H2 product and present metallurgical limitations, generally the single stage reforming is limited commercially to about 1,550 F. and 300 p.s.i.g.

In typical partial oxidation processes, a hydrocarbon is reacted with oxygen to yield hydrogen and CO. Insufficient oxygen for complete combustion is used. The reaction may be carried out with gaseous hydrocarbons or liquid or solid hydrocarbons; for example, with me With heavier hydrocarbons, the reaction may be represented as follows:

Both catalytic and noncatalytic partial oxidation processes are in use. Suitable operating conditions include temperatures from 2,000 F. up to about 3,200 F., and pressures up to about 1,200 p.s.i.g., but generally pressures between and 600 p.s.i.g. are used. Various specific partial oxidation processes are commercially available, such as the Shell Gasication Process, Fauser-Montecatini Process, andthe Texaco Partial Oxidation Process.

There is substantial CO in the hydrogen-rich gas generated by either 'reforming or partial oxidation. To convert the CO to H2 and CO2, one or more CO shift conversion stages are typically employed. The CO` shift conversion reaction is:

This reaction is typically effected by passing the CO and H2O over a catalyst such as iron oxide activated with chromium. The reaction kinetics are faster `at higher temperature, but the equilibrium to hydrogen is favored by lower temperatures. Therefore, it is not uncommon to have ahigh temperature shift stage followed by a low temperature shift stage. Pressure has little bearing on the equilibrium in the water-gas shift reaction.

B. CO2 or COz-i-HZS removal.-Because most hydrogen-using processes, particularly hydroconversion processes,` operate more eiciently with high purity hydrogen, it is generally required to remove impurities, such as CO2, from the raw hydrogen generated in the hydrogen plant before the hydrogen is passed to the hydrogen-using process. Perhaps the most widespread method of removing CO2 from' other gases is the absorption of CO2 in an alkanolamine, such as diethanolamine (DEA) or monoethanolamine (MEA). Largely because of its relatively low molecular weight, MEA is generally the preferred absorbent of the alkanolamines. The CO2 forms a loose chemical bond with the amine when it is absorbed.

In using any of the commonly used alkanolamine V,absorbents, an absorber and stripper are typically arranged in a gure eight process configuration. The f CO2-containing gas is fed into the bottom of the absorber where CO2 is absorbed in downward ilowing absorbent. Purified gas with the CO2 removed leaves the top of the absorber. -Rich absorbent from the bottom of the absorber is passed to the top of a stripping column where it is regenerated as it passes from the top to the bottom of the stripping column. The regenerated absorbent passes from the bottom of the stripper to the top of the absorber to complete the figure eight path of the absorbent as it flows down through'the absorber trays, or packing material, absorbing CO2. A large amount of heat is required to strip the CO2 from the MEA absorbent which is typically used because of the chemical bond that occurs between the CO2 and the MEA. For instance, in a large hydrogen plant producing 135 l06 standard cubic feet per day of hydrogen, over 300x106 B.t.u.s per hour are generally required to reboil the MEA in order to effect the regeneration of the MEA. These 300 106B.t.u.s per hour are equivalent to over 1,000,000 dollars per year in terms of steam (at 4a value of about 40 cents per thousand pounds) that could be generated.

-Over a period of time, a considerable amount of MEA will be lost out the top of the absorber as large volumes of gas carry entrained MEA out the top of the absorber in spite of preventive measures. Further MEA is lost due to pumping losses as large volumes of absorbent ae required and therefore circulated to remove the great quantities of CO2 that are typically formed in modern hydrogen production plants. Other common CO2 absorption systemfor example, hot carbonate-are generally similar to the alkanolamine system in the respects described above with only moderate reduction in regeneration heat requirements.

Since the alkanolamine absorbents tend to degrade, a reclaimer is commonly used to purify the absorbent. The reclaimer is essentially a small reboiler. It is fed a slipstream of the absorbent from the bottom of the stripper. Only that portion of the slipstream that is vaporized is returned to the stripper system. Heavy tarry material collects in the bottom of the reclaimer and is periodically withdrawn and passed to sewerage as a spent alkanolamine stream. Common practice is to clean the reclaimer as frequently as once a week. The cleaning procedure typically involves taking the reclaimer olfstream, draining the spent alkanolamine and heavy tarry material, and steam cleaning the reclaimer.

It is thus apparent that cleaning the reclaimer will result in losses of absorbent in addition to those losses caused by entrainment and pumping leakage. Although the alkanolamine is expensive, this cleaning procedure is necessary to avoid build-up of corrosive bodies in the CO2 absorption system. Corrosion, which would be worse without the reclaimer, still is a considerable problem in the alkanolamine CO2 absorption systems.

C. Compression of high purity hydrogen-Some of the processes which use high purity hydrogen as a reactant are: hydrodesulfurization, operating at pressures between about 100 and 1,500 p.s.i.g.; hydrotreating, operating at pressures between about 200 and 2,000 p.s.i.g.; hydrocracking, operating at pressures between about 450 and 3,000 p.s.i.g.; and thermal hydrodealkylation, operating at pressures between about 450 and 1,000 p.s.i.g. All of these just-mentioned hydroconversion processes may operate at even higher pressures (for example, up to 10,000 p.s.i.g.) than just given but seldom will operate at pressures lower than the range given. Thus it can be seen that many of the processes which use hydrogen require the hydrogen at a high pressure, which in most cases means generated hydrogen gas must be compressed before being passed to a hydrogen-using process.

Basically, all compressors may be considered as belonging to one of two categories; i.e., their principles involve either that of true mechanical compression (positive displacement) or centrifugal compression. Compressors utilizing true mechanicalV compression are so considered because the act of volumetric reduction is accomplished by means of a compressing element. The compression element may be in the form of a piston which in its particular motion entraps and displaces gas within a suitably designed'and fully enclosed housing. Motion may be reciprocating during which the element, in the form of a piston, passes back and forth within dimensional limits over the same course within a cylinder in a straight-line direction. j

Centrifugal compression is accomplished by centrifugal force exerted on an entrapped gas during rotation of an impeller athigh speed. Most centrifugal compressors depend primarily on centrifugal force and high tangential velocityy of the iuid-in the periphery of the impeller (or rotors or blades in the instance of some turbocom-y pressors) to produce the desired vhead or discharge pressure. In this specification, the terms centrifugal cornpression or compressor are meant to include turbine compression or turbocompressors, including, for example, axial-flow compressors. In the broad sense of centrifugal compression used herein compression is effected, at least to a substantial degree, by conversion of velocity head to pressure head.

The reciprocating compressor is used for hydrogen compression, but it has some severe disadvantages, particularly for large-size plants: p

(1) All parts are subject to unbalanced, reciprocating stresses; and foundations, frames and other parts must be large. To minimize vibration, speeds are low (400-700 r.p.m.); and capacity is low. Therefore, in large plants, several machines are required. Cost of installing, instrumenting, protecting and piping several machines is high. Considerable land is required, and plants are bigger and more complex, making them more difficult to control.

(2) The vreciprocating machine is less reliable than centrifugal machines, and it is common practice to design plants with one or two expensive spare machines ready to come on-stream in the event o fa failure.

(3) The reciprocating machine produces a pulsating gas supply which sonically transmits 'vibration-to piping instruments and other plant facilities. Such vibrations can cause hazards failures with' hydrogen as high pressure.

(4) The low speed of reciprocating compressors tends to limit prime movers to low speed, electric motors or gas engines. While it is possible to use high speed steam or gas turbines, large reduction gears must bel used. The pounding of the reciprocating loads has led to poor experience with these units. Hydrocracking and hydrogen' manufacturing processes can be designed to produce byproduct steam if it could be used in steam turbine drivers. However, for the reasons just given, this byproduct steam is generally not used to drive the reciprocating compressors.

(5) Reciprocating compressors are particularly susceptible to severe damage if liquid is present in the gas being compressed.

By comparison, centrifugal compressors are reliable, rugged, in most cases relatively simple, have large capacities, are relatively small, have balanced stresses, and generally cause relatively little vibration or pulsation in fthe plants. They can be driven by high speed, steam turbines or gas turbines. i

However, centrifugal compressors cannot, with any reasonable degree of feasibility, be used as high purity hydrogen compressors.

Compression ratios (ratio of discharge pressure to inlet pressure for one stage of compression) obtainable with a centrifugal compressor are a function of the molecular weight of the gas to be compressed. With pure hydrogen having a molecular weight of 2, compression ratios are limited to about 1.025. Because of this low compression ratio for hydrogen, centrifugal compressorsy are' not practical to date for compression of high purity hydrogen.

Table I below illustrates the sharp decrease incompression ratio for centrifugal compression Vas the molecular weight of the gas being compressed decreases. The number of stages used in the compression is the same for each case in Table I.

TAB LE I As previously indicated, it is not practical to use centrifugal compressors to compress high purity hydrogen to high pressures because of the multitude of stages that would be required. For example, the centrifugal compression ratio (ratio of discharge pressure to inlet pressure for one stage of centrifugal compression) with hydrogen, molecular weight of 2, is limited to about 1.025. Consequently, over 75 stages of centrifugal compression would be necessary to bring the pressure of hydrogen up to 1,700 p.s.i.g. starting from a pressure of 200 p.s.i.g. On the other hand, two stages of a reciprocating positive displacement compressor could increase the pressure from 200 p.s.i.g. to 1,700 p.s.i.g. Thus, in spite of their problems previously discussed, reciprocating compressors have here- 'tofore been used in bringing high purity hydrogen to high pressure.

SUMMARY OF THE INVENTION According to the present invention, an improved process is provided for manufacturing high pressure, high purity hydrogen which comprises:

(l) Generating at a pressure below about 450 p.s.i.g. a hydrogen-rich gas containing sufficient CO2 so that the molecular weight of the hydrogen-rich gas is at least four;

(2) Centrifugally compressing the hydrogen-rich gas from the pressure below about 450 p.s.i.g. to a substantially higher pressure above 450 p.s.i.g. to obtain high pressure hydrogen-rich gas;

(3) Removing CO2 from the high pressure hydrogenrich gas to obtain high purity hydrogen, at least part of the CO2 being removedy by absorbing CO2 in a physical absorbent.

Heretofore, centrifugal compression has not been used to bring high purity hydrogen to high pressures used, for example, in hydrocracking. This is because of the inapplicability of centrifugal compressors in compressing high purity hydrogen to high pressures, generally above 450 p.s.i.g., and most frequently above 900 p.s.i.g.

The present invention is based on the idea that the raw hydrogen may advantageously be compressed before CO2 removal thus making possible the use of a centrifugal compressor because of the higher molecular weight of the gas mixture of H2 and CO2. It is surprisingly found that, in spite of the facts that much'energy is expended in bringing the CO2 to a high pressure and what is desired is to bring only the high purity hydrogen to a high pressure since the CO2 will ordinarily be vented, the new method provides an over-all more advantageous process.

According to a preferred embodiment of the present invention, purified H2 gas is obtained by centrifugally compressing a raw, AH'2-rich gas containing CO2 to high pressure and then removing the CO2 at high pressure by cooling to condense out a portion of the CO2 and removing residual (left afterremoving the condensed liquid CO2) gaseous CO2 from the H2 gas using a physical absorbent to physically absorb the residual CO2. According to a preferred embodiment of the present invention as integrated with a hydrocon'version process, the purified H2 gas is reacted with hydrocarbons in a hydroconversion zone; and the hot eflluent from the hydroconversion zone is used to generate atleast part of the steam to drive the centrifugal compressors which are used to compress the raw, H2rioh gas containing CO2.

V Some of the more salient advantages realized in accordance with the present invention and preferred em'- bodiments of the present invention are:

(1) Centrifugal compression replaces reciprocating compression and the problems of reciprocating compression. Simpler, less expensive, more reliable plants result. Maintenance expenses, including labor and parts required to repair the positive displacement reciprocating compressors, are reduced. Also, the possibility and/or amount of production stoppage due to compressor breakdown is lgreatly reduced. Hazard due to equipment failure on high pressure equipment is decreased.

(2) Because the CO2 is brought to a high pressure as Well as the hydrogen, improve methods of removing CO2 t advantageously into the hydrogen productionscherne. For example, condensation of CO2 is attainable much more readily at the higher pressures because extremely low temperatures are not required. Initial condensation of CO2 is obtained by cooling to about 0 F. if the partial pressure of CO2 is at least 306 p.s.i.a. (306 p.s.i.a. corresponds to about 20 percent CO2 in a H2, CO2 gas mixture at 1,500 p.s.i.a.). Further condensation'is attainable by cooling to lowertemperature with the result that only a fraction of the original CO2 is left in the hydrogen-rich gas. Thus, in a preferred embodiment of the present invention, the CO2 absorption requirements of the absorbent are reduced as the absorbent only is required to absorb the fractional amount of CO2 left in the hydrogen-rich gas after condensation and separation of a large (e.g., from 25 to 95 percent, preferably about 50 `to 70 percent) portion of the CO2 in the raw, hydrogen gas mixture.

Since the absorption takes place at high pressures an since at least part of the CO2 is advantageously condensed at high pressures, much of the cooling required for the low temperature absorption can be obtained by subsequent reductions of pressure on the condensed CO2 and/or the CO2-rich absorbent. The absorbent is regenated primarily by expansion to a lower pressure. The description of the carbon dioxide effects substantial cooling of the absorbent and thus lowers the temperature of the absorbent which was earlier raised by the heat of absorbing CO2. Also the high pressure condensed CO2 separated from the raw hydrogen gas can be used to remove large quantities of heat from the feed to the CO2 absorber, as the condensed CO2 is expanded to substantially lower pressures and is therefore available as a refrigerant.

(3) Because of the high pressure obtained by centifugally compressing the H2 and CO2, nearly all of the CO2 may be removed from the H2 relatively easily by physical absorption of the C02.

In using the physical absorption, the solubility with respect to temperature Vand pressure follows the normal trends; that is, increased solubility with decrease in temperature or increase in pressure. Thus the high pressure works to the advantage of the absorption step in two respects. It increases the ability of the absorbent to absorb CO2 because of the high pressures. Also, since the high pressures result in a system that is easily completely or nearly completely self-refrigerated, low temperatures are economically obtainable so that the absorption may `be carried out atlow temperature where the solubility of `CO2 (or CO2 and H2S) in the absorbent is relatively high. The refrigerating of the absorption step is effected primarily by expansion of released CO2 which is desorbed from the high pressure, CO2-rich absorbent by reducing .the pressure on the CO2-rich absorbent.

The high pressure required in the absorption step o :the present invention generally is between about 450 p.s.i.g. and 4,000 p.s.i.g., but pressures as high as 5,000

to 10,000)".p .s,i.g. may be employed. However, the more usual .pressure range is betweenv 9 00 p.s.i.g. and 3,000

p.s.1.g.

v (4) Because of the improved methodsv of removing CO2, less Aheat is needed infthe CO2 4removal step. Specifically, less heat isneeded to regenerate the CO2 absorbent. This )isV ylargely l because the absorbent is Iregenerated Algrrjirnarily or, vin vsome instances solely by teducing'the pressure on the absorbent so as to4 release ythe CC,)2Whi ch` has been physically absorbed Yat, the high pressure obtained by centrifugalco'rnpres'sion of they H2- richga'sfcontaining CO2, K

(5) Sice`fless heatis needed', in `theCO2 removal step, which heatis generally' supplied by the eiiluen't from the steam 'reforming or partial oxidation zone, this effluent lheat is new used, for example, to generate steam which is readily useable-,in the, high speedturbine driving the high speed, raw` `hydrogen ygas centrifugal compressor or bmrressgr. j l f ,1(6)VX Heatavailable from' the effluent of a hydro-con- Yersionflzone using l'the' 'higlr purity, high pressure .A hydrogen vfrom 'the hydrogen production zone` can be used to gfener'ateesteam tofdrive the centrifugal compressor of the"hydro'g en productionzone.

'BRIEF-DESCRIPTION OF THE DRAWING The drawing isla rschematicflow sheet vof a preferred embodiment of the invented yprocess. The major process steps shownin the drawing include: facilities for generating yH2-ric`h gas containing CO2, steam boilers for producing steam tofdrive the centrifugal compressor, a centrifugal compressor for obtaining high 'pressurevHzrich gas containing CO2, "heat exchange for cooling the Ill2rich gas containing CO and condensing a part of the CO2, absorption facilities'for removing CO2 (or CO2 and H2S) from the H2-richvgas, and ahydroconve'rsion zone for reacting the puried H2 gas with hydrocarbons in reactors, with the hot effluent from these hydro'conversion reactors being used to generate steam to drive the centrifugal compressor.

DETAILED DESCRIPTION AND DESCRIPTION OF THE DRAWING Vz Referringv now in-more detail to the embodiment'of the'inventionshown in the drawing, partialoxidation or 7" steam reforming is carried out in accordance'with wellknown processes in zone 12. d y' In the case of partial oxidation, a hydrocarbon, which may be a gas, oil vor 'a' solid, is fed tothe partial oxidation zone through line 10. Steam and/ or oxygen isfed to the partial oxidation zone through line 11. Thehydrocarbon and oxygen are reacted in a partial oxidation reactor at elevated temperatures, either withonwithout catalyst, according to well-known processes to produce H2, CO and CO2. Pressure in the partial oxidation reactor typically is between 200 and 600 p.s.i.gtand temperature between 2,000 and 3,200 F. 5

H2S is formed in the partial oxidationvreaction inthe hydrocarbon feed to the partial oxidation reactor'cntains sulfur compounds. The H28 formed may be removed lbefore passing' the partial oxidation reactor *effluenty to the CO shift conversion reactor. If the partial oxidation Vof centrifugal compression for obtaining a"high pressure H24VCO2 gas mixture.

Because there are, however, sulfur resistantJ CO. shift be left in the hydrogen-rich gas feed to the CO shift converter. In this qcase, it is preferred to compress the H2-CO2-H2S gas mixture from the CO shift converter to high pressure and then remove the CO2 and H2S as b y physical absorption or a combination of condensation and physical absorption of the CO2 and HZS.

In the case of steam reforming, a desulfurized feedvstock is mixed with superheated steam and charged to a ,steam reforming furnace. The furnace consists of a combustion chamber in which are located alloy tubes containing a nickel base catalyst. While passing over the catalyst, the hydrocarbons are converted to H2, CO2, and CIO; The furnace supplies the heat needed to maintain the temperature for the endothermic reaction. Outlet temperature from the reforming furnace is usually maintained between 1,400-l,620 F., and pressure maintained between about 75 and 450A p.s.i.g. As` in the case of partial oxidation, ,carbon monoxide in the effluent hydrogen-rich gas from the steam reformer is reacted with water in one or `more shift reactors toproduce more H2 and CO2 and reduce the CO content to about 0.2-2 volume percent.` i

The raw Vhydrogen gas from zone 12 comprised predominantly of H2l and containing a minor amount of CO2 (and, in sOmecaSeS, also containing H25) passes via line 13 from the shift conversion step in zone 12 to a steam .boiler E-lvwhere'steam is generated from the boiler feed water` passed through lines 60 and 61 into E-1. The raw hydrogen gasmwhich'has been cooled insteam boiler E-1 passes through` water cooler 14 and then to separator 15. Water that has been condensed from the raw hydrogen gas is removed through line 70 and passed to further processing not shown. Th'e raw hydrogen gas is withdrawn from the separator through line 16 and passed to centrifugal compressor 17. The centrifugal compressor substantially increases the pressure of the H2, CO2 gas mixture; i.e., the pressure is increased by at least 200 p.s.i. Preferably the pressure is increased by 450 p.s.i., and still more preferably the pressure is increased by as much as 1,000 or v1,500 p.sLi. For example, when the raw hydrogen gas is generated by steam reforming, the pressure is advantageously raised from below about 45 0 p.s.i.g. to above about'900 p.s.i.g., preferably above 1,300 p.s.i.g.l Presence ofthe CO2 in the raw, hydrogen-rich gas that is passed to the centrifugal compressor not only increases the molecular weight' of the gas mixture but also increases Vthe volume ofthe gas mixture. Both of these factors increase the applicability of 'centrifugal compressorsas opposed to reciprocating.

In the preferred embodiment shown in the drawing, all of the gas .from H2 .manufacturing lzone 12 is passed to the centrifugal compressor.. Because of thel 17 to 40i volumeperce'nt CO2 present, along with other impurities .,suchpas CO, ,the moleculanweight of thisHZ-rich gas is between about 10 and. 25. .Within the concept of the present invention, it. is practicalto lower the .molecular weight of the H2-rich gasto as low asabout 4 by removing part of the CO2'fand thenusing centrifugal compressors for compression tovhigh pressure. Thus an alternate toY the embodiment of the present invention wherein the hydrogen-richgas is compressed before CO2 removal is centrifugal compression after partial vCO2 Iremoval but before' final CO2 removal. A gas mix-ture of H2 and CO2 `containing about 5 volume, kpercent CO2 has a molecular Weishtbf tout..v v l i High pressure, raw hydrogen gas is withdrawn from the centrifugal compressor through line 18 and cooled by heat exchange withcooling water in exchanger E-.3. To avoid icing, antifreeze is added through line 19 to the effluent rawhydrogen gas from E-3. Acetone or methano1, forexarnple, may be used as the antifreeze. Then the gas is/passedin line k21 through exchanger E-4 and further cooled by,a,refrigerant, for example, ammonia. The refrigerant will serve to remove imbalance head loads `from the-systemduring start-up and also to remove excess f heatk that is not removedlby i the .CO2 and. absorbent that are expanded after the CO2 absorption, as is described below. For purposes of illustration, methanol is used as the preferred absorbent in the description of the drawing, although other physical absorbentsmay be advantageously used.

As distiguished from chemical absorbents certain classes of materials are regarded as physical absorbents. Examples of physical absorbents are methanol, and other monovalent aliphatic alcohols, such as ethyl alcohol and propyl alcohol, or cyclic alcohols, such as cyclopentanol and cyclohexanol; aliphatic polyvalent alcohols, such as 'ethylene glycol, propylene glycol and glycerin; lower ketones, such as acetone, diethyketone, methylbutylketones; N-alkylated pyrrolidones, such as N-methyl pyrrolidone; N-alkylated piperidones; and sulfones, such as tetrahydrothiophene 1,1-dioxide and the homologues thereof; dialkyl ethers of a polyalkylene glycol such as the dimethyl ether of diethylene glycol, thedimethyl ether of triethylene glycol, the dimethyl ether of tetramethylene glycol, the dimethyl ether of pentaethylene glycol, the dimethyl ether of hexaethylene glycol, and the dimethyl ether of heptaethylene glycol. Particularly preferred physical absorbents for use in the present invention are propylene carbonate, acetone, and methanol.

Although according to a preferred embodiment of the present invention carbon dioxide is absorbed primarily by high pressure physical absorption, a minor amount of chemical absorbent may be mixed with the physical absorbent-for example, to increase the eiliciency in lowering the CO2 content in the H2 gas to very low concentrations. Thus where it is desired to reduce the CO2 concentration to about 500 p.p.m. by volume or lower, it is advantageous to mix with the physical absorbent certain chemical absorbents, such as alkanolamines or other compounds whose absorption mechanism involves the formation of salts or other decomposable reaction products; i.e., products which when heated decompose to release the chemically absorbed CO2 and thus regenerate the chemical absorbent. Among the alkanolamines which act as chemical absorbents, monoethanolamine and diethanolamine can be used with particular advantage. Other typical chemical absorbents are dipropanolamine, diisopropanolamine, alkyl phenyl alkyl amines, alkoxy alkyl amines and alkoxy aryl amines. In contrast to physical absorbents, chemical absorbents, such as MEA, have little increased ability to absorb CO2 at high pressures versus lower pressures of about 250 p.s.i.g;

The raw hydrogen gas passes in line 22 to exchanger E-S where it is further cooled by expanding CO2 that was previously condensed -by cooling the high pressure raw hydrogen gas. Thus expanding low temperature CO2 is used to cool high pressure raw hydrogen gas and condense CO2.

The raw hydrogen gas in line 23 from E-S then passe through B-6 where it is still further cooled (with resultant increased CO2 condensation) by exchange with the absorber overhead. The eiliuent from E-6, comprising H2, liquid CO2 or CO2 and H28, and residual CO2 or CO2 and H2S at a pressure of, for example, 1,700 p.s.i.g., is passed in line 24 to absorber 25. In absorber 25, CO2 or CO2 and I-I2S, that has -been condensed due to cooling in the preceding exchangers, drops to the bottom; and residual, gaseous CO2 or CO2 and H2S is absorbed in methanol absorbent and thus removed from the raw hydrogen gas as the gases pass upward in absorber 25. Hydrogen gas containing aboutv 1.0 percent CO2 and 1.0 to 2.5 percent CO by volume passes out the absorber in line 48. After transferring heat in exchanger E-6, the hydrogen gas stream is passed in line 49 to methanation zone 50.

Rich absorbent, laden with CO2 and possibly H2S, is removed along with condensed liquid CO2 in line 26 from the bottom of absorber 25. After reducing the pressure, the absorbent and liquid CO2 are passed in line 27 to first letdown drum 28 where a small Vamount of dissolved hydrogen is flashed off and removed in line 29. This hydrogen is recycled to the vcompressor for recovery lUl via line 7 0. Because the hydrogen is much more volatile and less soluble in the absorbent than CO2, the hydrogen may be removed as a gas while the CO2 remains in the liquid phase. The absorbent and liquid CO2 are passed from the lirst letdown drum in line 30 to expander 31 where the pressure is further reduced. The expander 31 recovers work energy from the expanding and vaporizing CO2, which work energy can be used, for example, to drive absorbent pump 36. CO2 and absorbent leave expander `31 in line 32 to second letdown drum 33. Low temperature, gaseous CO2 resulting from the expansion is withdrawn from the second letdown drum in line 34 and passed through E-5 countercurrent to high pressure H2- rich gas containing CO2 to remove heat from the H2-rich gas 'containing CO2. In the partial oxidation process, the CO2 in line 344 may contain H28; Aand it may be advantageousv to process this gas for H2S removal from the CO2 before warming in E5. This can be done in a separate columnA with a small stream of purified absorbent from line 47. CO2 is withdrawn from heat exchanger E-S in line 9 and vented or passed to further processing.

Methanol absorbent in line 35 from the bottom of the second letdown drum contains a small amount of CO2 not flashed `off as a gas in the second letdown drum. This absorbent, which has been cooled to about -80 F. due to CO2 -ashing olf from the absorbent, is passed in part to an intermediate point in absorber 25 via lines 37 and 38. Although the methanol absorbent in line 38 has not been completely freed of CO2, it still is effective to remove CO2 because of its low temperature (which tends toucondense CO2), as it is introduced to the absorber at a point where `the CO2 concentration is suciently high that there is ample driving force from the gas phase into the liquid CO2 absorbent phase. The remaining part of the absorbent is passed in line 39 through cooler E-7 into the top of absorbent regenerator 41 via line 40. The reboiled regenerator 41 frees this part of the absorbent of essentially all CO2 or CO2 and H2S remaining in the absorbent removed from the second letdown drum. The thus purified absorbent is withdrawn from absorbent regenerator 41 in line 46 at an intermediate position, below absorbent inlet line 40 but substantially above the bottom of regenerator 41. This lean absorbent is cooled to about -65 F. by passing through E-7 countercurrent to the regenerator feed. The lean methanol absorbent is withdrawn from E-7 in line V47 and passed to the top part of absorber 25.

Reboiling heat is supplied to the regenerator 41 by reboiler E-S, which reboils a portion of the regenerator bottoms using steam as a heating medium. A small amount of water is withdrawn from the bottom of regenerator 41 in line 43. CO2 is withdrawn in line 42 from the top of regenerator 41 as a gas and is vented orpassed to further processing. In the case where partial oxidation is used to generate the raw H2rich gas, typically the gas withdrawn in line 42 from regenerator 41 will contain H2S. In this instance, the gases from the regenerator may be passed to a Claus process for the production of sulfur if there is sufficient H28 in the CO2-H2S gas mixture in line 42.

In methanation zone 50, the CO and CO2 in the hydrogen-rich gas effluent from absorber 25 are converted to methane and steam by the following reactions:

High pressure, in excess of 450 p.s.i.g., favors the conversion of carbon oxides, in the methanation zone. High purity hydrogen, containing no more than 20 parts per million carbon oxides and about 4 percent other impurities, such as CH4, is withdrawn in line 51 from the methanation zone. It is passed together With recycle hydrogen throughline 53 `and 54 and reacted with hydrocarbons in the hydroconversion zone 55.

Alternatively to the methanation zone, a copper liquo system may be employed to remove CO, as the copper liquor systems are advantageously used at high pressure for absorbing CO so as to obtain high purity hydrogen. In general, the term high purity hydrogen connotes hydrogen purity of about 96 to 99+ volume percent, with the balance being impurities comprising CH4, N2 and small amounts of carbon oxides. But in some cases, the high purity hydrogen may contain 5 to 8 percent impurities by volume, particularly when the CH4 content is relatiwely high in the product hydrogen. The term high purity hydrogen is used to refer to the hydrogen either before or after methanation or alternative processing for reduction of the carbon oxides from small concentrations down to the parts per million level.

yHydrocarbon feed enters the hydroconversion zone through lines 52 and 54. The hydroconversion zone may, for example, be a hydrodesulfurization unit operated at about 1,700 p.s.i.g. and 700 F. reactor pressure and temperature, respectively, and consuming about 500 s.c.f. of hydrogen per barrel of hydrocarbon feed to the hydrodesulfurization unit. As indicated previously, other hydroconversion processes include hydrocracking, hydrotreating or hydrofining and thermal hydrodealkylation. The eluent from the hydroconversion zone, at temperatures between 40G-1,200 F., generally between 40G-800 F. is Withdrawn in line 56. This high temperature eluent stream is passed through steam boiler E-2 wherein heat is removed from the hydroconversion zone eluent to generate steam. The steam is generated from the boiler feed water passed through lines 60 and 62 into the steam boiler. Steam is withdrawn from steam boiler E-1 in line 64 and from steam boiler E-2 in line 63 and passed in line 65 to turbine driver 67. Thus steam is produced through heat recovery from the hydroconversion zone as well as from the hydrogen production zone to drive the turbine driver 67. The turbine driver 67 in turn furnishes the motive power for raw hydrogen gas centrifugal compressor 17. Either back pressure steam turbines or condensing steam turbines are used to drive compressor 17. Exhaust steam is Withdrawn from the turbine in line 66.

After heat is recovered from the hydroconversion zone effluent in steam boiler E-2, the effluent is passed in line -57 to` separator 58. Recycle hydrogen is withdrawn from the separator in line 68; and oil is withdrawn from the bottom of the separator in line 59 for further processing, such as fractionation or further hydroconversion.

Steam generated by the steam boilers in addition to that required by turbine driver 67 is Withdrawn in line 69 and is used to reboil the absorbent regenerator reboiler E-8 and to supply steam to partial oxidation or steam reforming zone 12. In the case of steam reforming, a large quantity of steam is generated by removing heat from the reforming reactor eiliuent prior to CO shift conversion. This steam may be used to drive turbine driver 67 and to supply steam needed for the steam reforming reaction. Exhaust steam from turbine driver 67 is used elsewhere or is condensed depending upon the design of the turbine driver.

EXAMPLE l The following example is based on calculated improvements (which could be made using the principles of this invention) to a new plant which produces 135 MM s.c.f.d. (million standard cubic feet per day) hydrogen.

Natural gas is fed in line 10 and steam in line 11 to a steam methane reformer furnace. Furnace eluent comprising H2, CO2 and CO is quenched by spraying water into the hot gas; and then the eiiuent is successively passed through a high temperature CO shift converter, a second water spray quencher, and a low temperature CO shift converter to convert Water and CO to CO2 plus hydrogen. A wet, gaseous stream at about 500 F. and containing about 80 percent hydrogen and 18 percent CO2 (dry basis) is then cooled in steam boiler E-l, rst generating 150 p.s.i.g. steam and then '40 p.s.i.g., and then heating boiler feed water. It is finally cooled With cooling water to condense most of the excess steam in the process gas. A total of about 340,000 1b./hr: of steam is recovered. When augmented with 20,000 lb./hr. of steam generated in steam boiler E-2 and used in turbine driver 67 (which exhausts to water-cooled condensers operating under vacuum), about 24,000 b.h.p. is produced. This is enough to drive centrifugal compressor 17 compressing the hydrogen and CO2 from a pressure of 225 p.s.i.g. to 1,700 p.s.i.g. Because of the reliability and large size of the centrifugal compressor, only one multistage unit is required.

CO2 is then removed from the high pressure gas in absorber 25 using semilean methanol at 90 F. in line 38 and lean methanol at F. in line 47. Semilean methanol is methanol which has not been completely regenerated and contains more CO2 than the essentially completely regenerated methanol withdrawn in line 46 from absorbent regenerator 41. At 1,700 p.s.i.g. pressure, the absorption system is essentially auto-refrigerated by expansion of the high pressure CO2. As explained under Detailed Description, the expanded CO2 is used to cool the Hz-COZ gas feed to absorber 25. Also, the methanol absorbent is cooled by the CO2 as CO2 flashes olf from the methanol as pressure is reduced in expanding the CO2- rich absorbent across expander 31. The small amount of CO and CO2 left in the gas from absorber 25 is converted to methane in methanator zone 50. High purity hydrogen is then fed at high pressure to hydroconversion zone 55 for upgrading hydrocarbons introduced in line 52.

In contrast, according to prior art, CO2 is removed from the H2, CO2 gaseous effluent from the CO shift converter using monoethanolamine (MEA) absorbent in an absorber operating at 250 p.s.i.g. Instead of using the heat in the HZ-rich gas prior to CO2 removal to generate 340,000 lb./hr. of steam to drive the compressors (as in the invention) in accordance with the prior art, the heat is used to reboil (regenerate) the CO2-rich MEA. To compress the high purity hydrogen according to the prior art, four reciprocating compressors are required (one spare). The three operating reciprocating compressors require 19,000 b.h.p. to compress the high purity hydrogen from 225 p.s.i.g. to 1,700 p.s.i.g. Cost of electricity con sumed by the electric motors used t0 drive the reciprocating compressors is $850,000 per year (19,000 h.p. .746 Kwhr./h.p. $7.22/ 1,000 Kwhr. 365 24 .95 Op. Factor).

In the present invention, heat is recovered from the hydroconversion zone 55 eiliuent to produce, in accordance with this example, about 20,000 pounds per hour of steam. This 20,000 pounds per hour is worth about $65,000/year. Making the conservative assumption that this 20,000 pounds per hour of steam could be utilized elsewhere, and also taking into account about $75,000 per year as the cost of steam for the absorbent regenerator of the present invention and for a small steam-driven refrigeration compressor used in the present invention, the net annual savings using the process of the present invention is $710,000 ($850,000-$65,000'-$75,000) for a hydrogen plant producing million standard cubic feet per day of hydrogen.

In addition to this $710,000 annual savings is the important reduction in plant complexity and improved maintenance and safety from the use of centrifugal compressors instead of reciprocating compressors used in the hydrogen production process of the prior art.

EXAMPLE 2 This example illustrates a preferred embodiment of the present invention wherein none of the CO2 is removed by condensation. More particularly, the present example summarizes estimated investment and operating costs calculated for a process in accordance with the priorart using monoethanolamine (MEA) for CO2 removal vs. a

1.3 vprocessain :accordance witha` preferred embodiment of the present invention using propylenevcarbonate for- CO2 remval^in va=75 MMs,c.f .d. per daysteam methane ,refor-ming hydrogen plant. The. MEA. absorbent i s\used in a conventional, chemical absorptionk system,... which is operatedat relatively lowpressures. The propylene carbonate absorbent tis; used in.afhighpressuretphysical absorption. system whichwca'n use a variety of solvents, such as methanol or acetone or n-methylpyrrolidone.

In either process, theeffiuent from the shift converter has the following composition `in moles, per hour; H2, 8,849; CO2, 2,253; CO, 28; N2, 51;v CH4, 227; H2O, 13; for a. total of 11,421. moles per. hour. The molecular weight of this gas mixture eiuent .from the COshift converter is-10.8. Thef-ar-nount of `the gas stream `in pounds per hour is thus about 123;000.'Thegas leaves .the `shift converter atapressuretof 250 p.s.i.g.

In theprocess according to the-prior lart usingMEA absorbent` for-removal of CO2, thiszgasumixtureat 250 p.s.i.g. is passed toa CO2' absorber .whereintMEA removes the CO2 from the hydrogen-rich gas mixture -by ychemical absorption of the CO2. High` purity hydrogen obtained from Vthe top of the CO,` absorber isccompressed by reciprocating compressors to '1,085 p.s.i.g. so'that'the pressure of the high'purity.-hydrogenishgh,enough for use in .a hydrocracking unit. zThe-MEAv absorbent isvregenerated; that is', C02 is removed from/theJMEA by stripping vin a 'CO2 stripper. The C02 stripper uses apsteam reboiier to generate hot stripping vapors in the bottom of the CO2 stripper land decomposerthe MEA-CO2 chemical bond at atemperaturetof Vabout 2005, F. The stripped MEA is removed from the bottom of the stripper, cooled taboutj 100 F., and "pfassed to the upper part of the CO2 absorber. 'i Y s l i For application of the propylene carbonate removal process in accordance with a preferred embodiment of the present invention, the hydrogemrich gas eluent from the CO shift converter having a molecular Weight of 10.8 is centrifugally compressed to a pressure -of 1,1101\p.s.i'.g. The temperature of the compressed hydrogen-rich gas is 110 F. This high pressure feed gas is partially dehydrated by glycol injection before CO2 removal both t0 avoid hydrates and to maintain the solvent in a nearly anhydrous state.

In order to take advantage of the physical absorbents higher CO2 capacity at lowered temperatures and to minimize absorbent vaporization losses, the absorption operation is caused to take place at reduced temperatures. This is accomplished by the use of a small propane refrigeration system. Thus the high pressure hydrogen-rich feed gas is cooled to labout F. and then fed to the CO2 absorber wherein cold propylene carbonate absorbs CO2. The propylene carbonate absorbent is both regenerated and cooled to about 0 F. by reducing the pressure on the CO2-rich absorbent withdrawn from the bottom of the CO2 absorber. Purified hydrogen exits from the top of the CO2 absorber at about 12 F. The purified hydrogen passes in counter-current heat exchange with the centrifugal compressor hydrogen-rich gas eiuent so that the purified hydrogen gas stream is heated to 80 F. The pressure of the purified hydrogen-rich gas stream after this heat exchange is about 1,085 p.s.i.g. The composition in moles per hour is: H2, 8,689; CO2, 90; CO, 28; N2, 51; CH4, 227; for a total of 9,085 moles per hour. The molecular weight of this purified hydrogen stream is about 3.01. So that the purified hydrogen will be more suitable for use in a hydrocracker, the purified hydrogen stream is passed to a methanator for conversion of CO2 and CO to CH4.

Table II below shows that the propylene carbonate systern operating at 1,100 p.s.i.g. has an estimated savings of $1.96 M in investment and four-year operating costs when compared with an optimistic MEA system. When compared with an MEA system which has a CO2 pickup of. 0.4 molejCOz per mole MEA (which is more in line yyitlractualpperating experience), the savings are about `$2.63 estimate is indicative of the savings that canberealized from a process which first compresses the shift converter ellluent gases and then removes the CO2 by high pressure physical absorption.

The use of centrifugal compressors contributes a major portion of the savings obtained according to the present invention.,For.the estimates in Table II, the propylene carbonate process is based on the centrifugal compressor operating at ,68 percent efficiency to compress the CO2- containing gas from about 250 p.s.i.g. to 1,110 p.s.i.g. An .investment cost of $260 per brake horsepower was used for the reciprocating compressor used to compress purified hydrogen obtained after CO2 removal using MEA absorbent. f n f ,.lflfhe hydrogen stream obtained after physically absorbing the-CO2 in a propylene carbonate absorbent contains labout l-percent CO2 impurity. After methanation, the hydrogen purity is thus about 1 percent less than for an MEA lsystem which removes essentially all of the CO2.

TEBLE rooz REMOVAL AND m ooMPREssroN FACILI- `TrEsrsM sono. HYDROGEN PLANT oosT ESTIMATES 1N THOUSANDS oF DOLLARS Propylene M Optimistic carbonate absorbent 1 MEA ababsorbent at at 250 sorbent 2 at A 1,100 p.s.i.g. p.s.i.g. 250 p.s.i.g.

.Onplotjnvestmentz CO2 removal 1, 350=l=300 1, 900 1, 660 Compressors 1, 720 3, 000 3, 000 Hydrocracker, incremental l 50 Total 3, 1201300 4, 900 4, 660

Fouryear operating costs power (0.722 cents/kwh):

CO2 removal 500 160 130 Compressors- 2, 470 1, 560 l, 560 Steam (40 ceutS/1,0001b.). 60 2, 460 1, 960 Hydrogen loss (35 cents] Total 3, 230 4, 3, 650

Investment plus four-year operating costs 6, 350i300 9, 080 8, 310 Incremental investment plus four-year operating costs..- 0 2, 630 1, 960

l Based on 20 Wt. percent MEA aqueous solution and CO2 pickup oi 0.4 mole G01/mole MEA.

2 Based on 20 wt. percent MEA aqueous solution and CO2 pickup of 0.5 mole C02/mole MEA.

l The propylene carbonate process requires an increased hydrocracker investment because hydrogen purity decreases by about 1%. The C02 impurity could be reduced if a mixture of propylene carbonate with a chemical absorbent is used as the absorbent.

It is to be understood that the forms of the invention shown and described herein are to be taken only as preferred embodiments. Various changes may be made while still remaining within the spirit and essence of the invention, such as in the arrangement of heat exchangers shown in the drawing, particularly those used to cool the effluent from the centrifugal compressor; the methanation step may be omitted where it is found preferable to produce H2 containing residual amounts of CO and CO2 rather than CH4; the CO2 may be removed in two or more absorbers with, for example, centrifugal compression and/ or low temperature CO shift conversion between CO2 absorbers; excess steam may be withdrawn from the steam system at various points other than indicated; and the steam may be used for additional functions, such as driving the absorbent pump instead of using the expander for this service. The invention may advantageously be applied in different embodiments than shown where it is desirable to obtain high pressure, high purity hydrogen.

- Accordingly, the invention is not to be construed las limited to the specific embodiments illustrated but only as defined in the appended claims.

We claim: 1, In a process for manufacturing high purity hydrogen by a train of steps comprising reacting hydrocarbons with oxygen-affording gas at conditions including a, pressure below about 900 p.s.i.g. and elevated temperature to -form a gas mixture comprising H2, CO and CO2, reacting CQ in the mixture with H2O to form additional H2 and CO2, and removing 4the CO2, to provide high purity hydrogen, the improvement for providing the high purityhydrogen at elevated pressure which comprises centrifugally ycompressing the gas mixture comprising H2 and CQz from the pressure below about 900 p.s.i.g. to a substantially higher pressure above 900 p.s.i.g., then removing CO2 from the compressed gas by absorbing CO2 in a physical absorbent at a pressure above 900 p.s.i.g. to thus obtain high purity hydrogen.

2. A process for manufacturing high pressure, high purityhydrogen which comprises: (a) generating by partial oxidation orf hydrocarbons at a pressure between 100 p.s.i.g. and about 1,'200

p.s.i.g. a hydrogen-rich gas containing sufficient C02` so that the molecular weight of the hydrogen-rich 3 (c) removing CO2 from the high pressure hydrogenrich gas to obtain high purity hydrogen, at least part of the CO2 being removed by absorbing vCO2 in a physical absorbent. e

-, t 16 e 3. Aprocess .for manufacturing high pressurel,r' 'high purity hydrogen which comprises:

(a) generating by steam reforming of hydrocarbons at y a pressure below about 450 p.s.i.g. a hydrogen-rich i, n gas containing suflicient'COg so that thelmolecular ,A weight of the hydrogenrich gas is at least-four; v(b) centrifugally compressing the hydrogen-rich gas from the pressure below about 450 p.s.i.g.` to a substantially higher pressure above 450 p.s.i.gl to obtain high pressure hydrogen-rich gas; 7 (c) removing ICOBfrom thehigh pressure hydrogen- ,rich gas to obtain high purity hydrogen, atleast part of the CO2 being removed by absorbing CO2 ina Y e physical absorbent. i i

4. A process formanufacturing` purity hydrogen which comprises:

(a) generating by partialf'oxidation of hydrocarbons at a pressurebelow about 450 p.s.i.g. a hydrogenrich gascontaining sufficient CO3 so that the molecular weight of the hydrogen-rich gas is at least four; (b) centrifugally compressing the hydrogen-rich gas from the pressure below about 450 p.s.i.g.y to a substantially higher pressure above 450 p.s.i.g. to obtain high pressure hydrogen-rich gas; l (c) removing C02 from the high pressure hydrogenj rich gas to obtain high purity hydrogen, at least part Yof vthe CO2 being removed by absorbing CO2 in a physical absorbent. u

high pressure, high References Cited UNITED STATES PATENTS 4/ 1971 Smith et al. 423-655 3,719,749 3/ 1973 Smith et al. 423-655 3,618,331 5/ 1968 Smith et al. 6'2-23 EDWARD STERN, Primary Examiner U.S. Cl. X.R. i

PO-OU C UNTTED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Parent No. 3,801,708 Dated April 2,19714 nventof) calvin s. smi-th and william J. McLeod Et ie certified that exray: in 'the ebove-idented Paten?. and that sec Lettere Peten: are hereby enneete es ehm-m zelow:

V-Col. l, line 7,0, secondary furnace" should read --secondary reforming furnace.

Col. 1+, line 39, "o fa" Should read --of a.

Col. 6, line 18, "improve" should read -mpr\o ved. Col. v.6, line 27, "temperature" should read temperatur-es. Col. 6, line -"lnegenerlted" should read --regenerated--L Col. 6, line 535l#, "centfugally" should read eentrfugally.

co1. 7, line 3u ."co" should read --co2. C

co1. 7, line ,'57, f'in" should read if- Col. 8, line 61, "volume, percent" should read --volumepercent--w Col. 8, line 72, "head" should read heat.

Col. 9, line 5, "dstigushed" should read --ds-tinguished". Col. 9, line l2, "diethyketone" shouldread diethylketone. Col.V 9, line 18, "tetramethylene" should read -tetraethylene.

Col. l0, line 1, "line 70" should read --line 7l-.

Col. 1M, line 3l, "Table I" should read Table I.

Signed and sealed this 22nd day of October 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Coxmniasioner of Patents 

